Iridium-rhodium alloys

Iridium-rhodium alloys were prepared in electric arc furnace in argon atmosphere by smelting refined powders of rhodium and iridium of 99.95 mass% purity. The composition of the alloys was controlled by the atomic adsorption analysis using the Perkin-Elmer spectrophotometer with HUS-72 analyzer. X-ray phase analysis indicated that all binary systems had a single-phase FCC-structure characteristic of... 

Hayhurst, A. N., and Kittelson, D. B. "Heat and Mass Transfer Considerations in the Use of Electrically Heated Thermocouples of Iridium versus an Iridium/Rhodium Alloy in Atmospheric Pressure Flames." Combustion and Flame 28 (1977) 301-17. 

Blackburn, G. F, and Galdwell, F. R. Reference Tables for Thermocouples of Iridium-Rhodium Alloys Versus Iridium, / Research of National Bureau of Standards—C. Engineering and Instrumentation 68C, no. 1 (1964) 41-59. 

Alloys with iridium Iridium alloys with platinum in all proportions, and alloys containing up to about 40% iridium are workable, although considerably harder than pure platinum. The creep resistance of iridium-platinum alloys is better than that of rhodium-platinum alloys at temperatures below 500°C. Their stability at high temperatures, however, is substantially lower, owing to the higher rate of formation of a volatile iridium oxide. 

Platinum and rhodium-platinum and iridium-platinum alloys are frequently employed to line and sheath autoclaves, reactor vessels and tubes, and a wide range of equipment. Linings are generally 0-13 mm to 0- 38 mm thick, and for certain applications co-extruded platinum-lined Inconel or other metal reactor or cooling tubes are fabricated. In such cases the platinum is bonded to the base metal, but in all other instances platinum linings are of the loose type. 

Some of the materials that have been examined as catalysts include Pure Platinum, Platinum-Iridium Alloys, Various Compositions of Platinum-Rhodium Alloys, Platinum-Palladium Alloys, Platinum-Ruthenium Alloys, Platinum-Rhenium Alloys, Platinum-Tungsten Alloys, FejOj-M CVI Oj (Braun Oxide), CoO-Bi20j, CoO with AI2O3, Thorium, Cerium, Zinc and Cadmium. 

Next, there is a block comparing palladium-iridium with all other catalysts except palladium (already considered). In this case, the gap between palladium-iridium and it is nearest rival (iridium) is just a little too small to be statistically significant however, the alloy was shown to be superior to the other two metals. For all the remaining comparisons among iridium, rhodium and platinum, the interval includes zero and they are non-significant. 

Detection of Ruthenium in Platinum Alloys.—In order to detect the presence of ruthenium in platinum alloys, a portion of the alloy is fused with lead. The melt is extracted with nitric acid and the residue ignited in contact with air in order to volatilise the osmium. The mass may now contain platinum, iridium, rhodium and ruthenium, and is fused with potassium nitrate and hydroxide. The whole is dissolved in water, treated with excess of nitric acid and allowed to stand in a flask covered with filter-paper. In a few hours (12-24) the filter-paper darkens if ruthenium is present, in consequence of the evolution of vapour of its tetroxide. To confirm the presence of ruthenium, the paper is ignited and the ash fused with potassium nitrate and hydroxide. On extraction with water the orange colour of potassium ruthenate is obtained.1... 

Jia M., Korenovsky N. L., Meretsky A. M., The features of hydrogen adsorption on iridium- rhodium metallurgical alloys during electrolysis of sulphuric acid solutions. J. Phys. Chem. 71 (1997) pp. 2044-2047 (in Russian). 

Rhodium and iridium are very unreactive metals, not being attacked by aqua regia (a mixture of nitric acid and sulfuric acid). Iridium is alloyed with platinum to produce a ery hard alloy, which is used for the tips of gold pens, surgical tools, and scientific apparatus. Representative compounds are Rb.Og, KgRbCl, Iro 3 and... 

The platinum-group metals (Ru, Os, Rh, Ir, Pd and Pt) are rare (Figure 23.1) and expensive, and occur together either native or in sulfide ores of Cu and Ni. Three sites of mineral deposits in the former Soviet Union, Canada and South Africa hold the world s reserves. The main source of ruthenium is from wastes from Ni refining, e.g. from pentlandite, (Fe,Ni)S. Osmium and iridium occur in osmiridium, a native alloy with variable composition 15-40% osmium and 80-50% iridium. Rhodium occurs in native platinum and in pyrrhotite ores (Fei S, n = 0-0.2, often with <5% Ni). Native platinum is of variable composition but may contain as much as 86% Pt, other... 

Alloys suitable for castings that ate to be bonded to porcelain must have expansion coefficients matching those of porcelain as well as soHdus temperatures above that at which the ceramic is fired. These ate composed of gold and palladium and small quantities of other constituents silver, calcium, iron, indium, tin, iridium, rhenium, and rhodium. The readily oxidi2able components increase the bond strength with the porcelain by chemical interaction of the oxidi2ed species with the oxide system of the enamel (see Dental materials). 

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

High Temperature Properties. There are marked differences in the abihty of PGMs to resist high temperature oxidation. Many technological appHcations, particularly in the form of platinum-based alloys, arise from the resistance of platinum, rhodium, and iridium to oxidation at high temperatures. Osmium and mthenium are not used in oxidation-resistant appHcations owing to the formation of volatile oxides. High temperature oxidation behavior is summarized in Table 4. 

Iridium [7439-88-5] Ir, and rhodium [7440-16-6] Rh, iadividually iacrease corrosion resistance, hardness, and strength of platinum alloys. They can be used to reduce grain size (140). 

Iridium on valve metals is suitable if the consumption rate of platinum is too high at elevated temperatures or critical composition of the medium. Mostly platinum-iridium alloys are used with about 30% Ir, because coating valve metals with pure iridium is somewhat complicated. For the same reason, other noble metals such as rhodium cannot be used [21]. At present there is little price difference between platinum and iridium. 

In 1996, consumption in the western world was 14.2 tonnes of rhodium and 3.8 tonnes of iridium. Unquestionably the main uses of rhodium (over 90%) are now catalytic, e.g. for the control of exhaust emissions in the car (automobile) industry and, in the form of phosphine complexes, in hydrogenation and hydroformylation reactions where it is frequently more efficient than the more commonly used cobalt catalysts. Iridium is used in the coating of anodes in chloralkali plant and as a catalyst in the production of acetic acid. It also finds small-scale applications in specialist hard alloys. 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Rhodium and iridium have a resistance to anodic corrosion comparable with that of platinum, and are more resistant to the influence of alternating currents. A platinum-iridium alloy, in the form of a coating on titanium, is preferred to pure platinum for the production of chlorine from brine , due to its improved corrosion resistance and lower overvoltage. 

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